JP2002128788A - Silicon-containing alicyclic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new silicon-containing alicyclic compound useful as a raw material for polysiloxane resins used for chemical amplification resists having excellent dry etching resistance, transparency to radiation, resolution, a developing property. SOLUTION: This silicon-containing alicyclic compound has such a structure that 2-hydroxy-(2-trifluoromethyl)ethyl group, 2-hydroxy-2-methyl-(2- trifluoromethyl)ethyl group or 2-hydroxy-2,2-di(trifluoromethyl)ethyl group and a (substituted) silyl group or cyclic polysiloxane group (the number of silicon atoms being 3-10) are bound to a bicyclo[2.2.1]heptane ring or 2-4 bicyclo[2.2.1]heptane rings-condensed ring, or a structure that the hydrogen atom(s) of the hydroxy group(s) in the above structure is (are) substituted with acid-dissociable organic group(s).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicon-containing alicyclic compound and, more particularly, to a raw material of a polysiloxane resin used for a chemically amplified resist suitable for fine processing using various radiations. The present invention relates to a novel silicon-containing alicyclic compound having a useful acid-dissociable organic group, and a novel silicon-containing alicyclic compound useful as a raw material of the silicon-containing alicyclic compound.

[0002]

2. Description of the Related Art In recent years, demands for higher density and higher integration of LSIs (highly integrated circuits) have been increasing, and accordingly, miniaturization of wiring patterns has been rapidly progressing. As one of means that can cope with such finer wiring patterns, there is a method of shortening the wavelength of exposure light used in a lithography process.
m) and i-rays (wavelength 365 nm)
rF excimer laser (wavelength 248 nm) or Ar
F deep UV or excimer laser (wavelength 193 nm), has been studied for the use of an electron beam, and so the X-ray or the like is used, also F ₂ excimer laser (wavelength 157 nm). By the way, novolak resins, poly (vinylphenol), and the like have been used as resin components in conventional resist compositions, but these materials contain an aromatic ring in the structure and have strong absorption at a wavelength of 193 nm. Therefore, in a lithography process using an ArF excimer laser, high sensitivity corresponding to high sensitivity, high resolution, and high aspect ratio cannot be obtained. Therefore, 193 nm
In the following, a resist resin material which is transparent particularly to a wavelength of 157 nm and has a dry etching resistance equal to or higher than that of an aromatic ring is required. One such example is a siloxane-based polymer. MIT RRKunz et al.
It has been reported that a polysiloxane-based polymer has excellent transparency at a wavelength of 193 nm or less, and that the polymer is suitable as a resist material in a lithography process using a wavelength of 193 nm or less (J . Photopolym. Sci. Technol., Vol.12, No.
4, 1999). It is also known that a polysiloxane-based polymer has excellent dry etching resistance, and in particular, a resist containing a polyorganopolysilsesquioxane having a ladder structure has high plasma resistance.

On the other hand, some resist compositions using siloxane polymers have already been reported. That is, JP-A-5-323611 discloses that an acid-dissociable group such as a carboxylic acid ester group or a phenol ether group is bonded to a silicon atom via one or more carbon atoms, and the side chain has an acid-dissociable group. Japanese Patent Application Laid-Open No. 8-160623 discloses that a carboxyl group of poly (2-carboxyethylsiloxane) is protected by an acid-dissociable group such as a t-butyl group. Positive resists using polymers are further disclosed in
No. 0733 discloses a resist resin composition using a polyorganosilsesquioxane having an acid dissociable ester group. However, a conventional resist composition using an acid-dissociable group-containing siloxane-based polymer is still unsatisfactory in terms of basic physical properties as a resist such as transparency to radiation, resolution, and developability.
Therefore, there has been a strong demand for the development of a new resin which provides a resist composition having excellent basic physical properties as a resist while having excellent dry etching resistance of a siloxane-based polymer, and a raw material compound for providing the resin.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a highly suitable material for a polysiloxane resin used in a chemically amplified resist excellent in dry etching resistance, transparency to radiation, resolution, and developability. Another object of the present invention is to provide a novel silicon-containing alicyclic compound which is useful as a raw material for polysiloxane resins and various silane-containing alicyclic compounds in other technical fields.

[0005]

The present invention comprises, first, a silicon-containing alicyclic compound represented by the following general formula (I) (hereinafter, referred to as "compound (I)").

[0006]

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[In the general formula (I), each R independently represents a hydrogen atom or a methyl group, and each R ¹ independently represents a hydrogen atom or a monovalent monovalent having 1 to 20 carbon atoms. A hydrocarbon group; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms;
A halogen atom; or a primary, secondary or tertiary amino group, wherein each R ² is independently of each other a monovalent hydrocarbon group having 1 to 20 carbon atoms; A halogenated hydrocarbon group; or the following formula (i)

[0008]

Embedded image (Wherein each X is independently a hydrogen atom;
20 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms.
It is an integer of 0. )

Wherein m is 0 or 1, two R ^{2 s} may be mutually bonded to form a ring with two oxygen atoms and a silicon atom, and Rf is hydrogen Represents an atom, a methyl group or a trifluoromethyl group;
Is an integer of 0 to 3, n is an integer of 0 to 3, and the silicon atom represented by the general formula (I) is the 2-position of the bicyclo [2.2.1] heptane ring at the highest position or It is bonded to the 3-position. ]

The present invention secondly comprises a silicon-containing alicyclic compound having an acid-dissociable organic group represented by the following general formula (II) (hereinafter, referred to as "compound (II)").

[0011]

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[In the general formula (II), each R independently represents a hydrogen atom or a methyl group; each R ¹ independently represents a hydrogen atom or a monovalent monovalent having 1 to 20 carbon atoms. A hydrocarbon group; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms;
A halogen atom; or a primary, secondary or tertiary amino group, wherein each R ² is independently of each other a monovalent hydrocarbon group having 1 to 20 carbon atoms; A halogenated hydrocarbon group; or the following formula (i)

[0013]

Embedded image (Wherein each X is independently a hydrogen atom;
20 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms.
It is an integer of 0. )

When m is 0 or 1, two R ^{2 s} may be mutually bonded to form a ring together with two oxygen atoms and a silicon atom, and Rf is hydrogen An atom, a methyl group or a trifluoromethyl group;
Represents a monovalent acid-dissociable organic group, m is an integer of 0 to 3, n is an integer of 0 to 3, and the silicon atom represented by the general formula (II) is a bicyclo [ 2.2.1] attached to the 2- or 3-position of the heptane ring. ]

The present invention provides, thirdly, a silicon-containing alicyclic compound represented by the following general formula (III) (hereinafter referred to as “compound (II)
I) ". ).

[0016]

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[In the general formula (III), each R independently represents a hydrogen atom or a methyl group, and each Y independently represents a hydrogen atom or a monovalent carbon atom having 1 to 20 carbon atoms. A hydrogen group; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; a halogen atom; a primary, secondary or tertiary amino group; or -OR ² , wherein R ² is 1 to 20 carbon atoms. Divalent hydrocarbon group; monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or the following formula (i)

[0018]

Embedded image (Wherein each X is independently a hydrogen atom;
20 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms.
It is an integer of 0. )

The group represented by And Rf represents a hydrogen atom, a methyl group or a trifluoromethyl group,
p is an integer of 3 to 10, n is an integer of 0 to 3,
Each silicon atom represented by the general formula (III) is a 2-position or 3-position of the bicyclo [2.2.1] heptane ring at the top.
Bound to the position. ]

The present invention fourthly comprises a silicon-containing alicyclic compound having an acid dissociable organic group represented by the following general formula (IV) (hereinafter, referred to as "compound (IV)").

[0021]

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[In the general formula (IV), each R independently represents a hydrogen atom or a methyl group, and each Y independently represents a hydrogen atom or a monovalent carbon atom having 1 to 20 carbon atoms. A hydrogen group; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; a halogen atom; a primary, secondary or tertiary amino group; or -OR ² , wherein R ² is 1 to 20 carbon atoms. Divalent hydrocarbon group; monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or the following formula (i)

[0023]

Embedded image (Wherein each X is independently a hydrogen atom;
20 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms.
It is an integer of 0. )

The group represented by And Rf represents a hydrogen atom, a methyl group or a trifluoromethyl group,
Z represents a monovalent acid-dissociable organic group, p is an integer of 3 to 10, n is an integer of 0 to 3, and each silicon atom represented by the general formula (IV) is at the highest position Bicyclo [2.2.
1] attached to the 2- or 3-position of the heptane ring. ]

Hereinafter, the present invention will be described in detail. Compound (I) In the general formula (I), R¹And R^Two1 to 2 carbon atoms
Examples of the monovalent hydrocarbon group of 0 include a methyl group and an
Tyl group, n-propyl group, i-propyl group, n-butyl
Group, 2-methylpropyl group, 1-methylpropyl group, t
-Butyl group, n-pentyl group, neopentyl group, n-
Xyl group, n-heptyl group, n-octyl group, 2-ethyl
Ruhexyl group, n-nonyl group, n-decyl group, n-dode
A sil group, an n-tetradecyl group, an n-hexadecyl group, n
-Octadecyl group, cyclobutyl group, cyclopentyl
Group, cyclohexyl group, etc., linear, branched or cyclic
Alkyl group; phenyl group, o-tolyl group, m-tolyl
Group, p-tolyl group, benzyl group, phenethyl group, 1-na
Aromatic hydrocarbon groups such as a futyl group and a 2-naphthyl group; nor
Bornyl group, tricyclodecanyl group, tetracyclodeca
And a bridged hydrocarbon group such as an enyl group and an adamantyl group.
Can be Of these monovalent hydrocarbon groups, R
¹As a methyl group, an ethyl group, a cyclopentyl group,
Cyclohexyl group, norbornyl group, tetracyclodeca
And the like.^TwoAs a methyl group, d
Til, n-propyl, i-propyl and the like are preferred.
No.

The monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms of R ¹ and R ² includes, for example,
A group in which a divalent hydrocarbon group is substituted with one or more or one or more halogen atoms, preferably one or more fluorine atoms,
More specifically, a trifluoromethyl group, a pentafluoroethyl group, 3,3,3,2,2-pentafluoro-n
-Propyl group, perfluoro-n-propyl group, perfluoro-i-propyl group, pentafluorophenyl group,
Pentafluorobenzyl group, pentafluorophenethyl group, perfluoronorbornyl group, the following formula (ii)

[0027]

Embedded image (In the formula, each Rf 'independently represents a hydrogen atom or a fluorine atom, and at least one Rf' is a fluorine atom, and b is an integer of 0 to 4.) And the like.

Among these monovalent halogenated hydrocarbon groups, a trifluoromethyl group, a pentafluoroethyl group,
3,3,3,2,2-pentafluoro-n-propyl group, pentafluorophenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, 2,3-difluorophenyl group, , 4-difluorophenyl group, 2,5-difluorophenyl group, 2,6
-Difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,3,6-triphenyl group Fluorophenyl group, 2,4
A 6-trifluorophenyl group, a 3,4,5-trifluorophenyl group, a pentafluorobenzyl group, a pentafluorophenethyl group and the like are preferable.

Examples of the halogen atom for R ¹ include a fluorine atom, a chlorine atom, and a bromine atom. Of these halogen atoms, a chlorine atom is preferred. Examples of the secondary or tertiary amino group for R ¹ include a methylamino group, an ethylamino group, an n-propylamino group, an i-propylamino group, an n-butylamino group, a cyclopentylamino group, and a cyclohexylamino. Group, phenylamino group, benzylamino group, dimethylamino group, diethylamino group, di-i-propylamino group, dicyclopentylamino group, dicyclohexylamino group, diphenylamino group, dibenzylamino group and the like. As the amino group for R ¹ , an amino group, a dimethylamino group, a diethylamino group, a dicyclopentylamino group, a dicyclohexylamino group, a diphenylamino group and the like are preferable.

In the formula (i) representing R ² , X is a monovalent hydrocarbon group having 1 to 20 carbon atoms;
Examples of the 20 monovalent halogenated hydrocarbon group include, for example,
The same groups as the monovalent hydrocarbon group and the monovalent halogenated hydrocarbon group exemplified for R ¹ and R ² can be exemplified. Among these groups, the monovalent hydrocarbon group is preferably a methyl group, an ethyl group, a phenyl group, etc., and the monovalent halogenated hydrocarbon group is preferably a trifluoromethyl group, a pentafluoroethyl group, a pentafluoro group. A phenyl group is preferred.

Examples of the linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms of X include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy group, sec-butoxy group, t-butoxy group, cyclopentyloxy group,
Examples include a cyclohexyloxy group. Among these alkoxyl groups, a methoxy group, an ethoxy group and the like are preferable. X in the formula (i) is particularly preferably a methyl group, a phenyl group, a methoxy group or the like. Further, a in formula (i) is particularly preferably 1 to 5.

R ¹ in the general formula (I) is particularly preferably a methyl group, an ethyl group, a cyclohexyl group, a phenyl group, a pentafluorophenyl group, a chlorine atom, a dimethylamino group and the like. Further, R ² in the general formula (I)
As particularly, a methyl group, an ethyl group, a t-butyl group,
Trimethylsilyl groups and the like are preferred. In addition, the general formula (I)
Is preferably both a hydrogen atom and a methyl group. Further, as Rf in the general formula (I),
A hydrogen atom, a methyl group and a trifluoromethyl group are all preferred. Further, m and n in the general formula (I)
Is particularly preferably 0 or 1, respectively.

Preferred specific examples of compound (I) include:
Formulas (I-1-1) to (I-1-36) shown below, wherein Rf represents a hydrogen atom, a methyl group or a trifluoromethyl group;
Represents a methyl group. The same applies hereinafter. ), Formulas (I-2-1) to (I
-2-44), Formulas (I-3-1) to (I-3-4), Formulas (I-4-1) to
The compound represented by (I-4-4) can be mentioned.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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Among these compounds (I), in particular, the compounds represented by the formulas (I-1-2), (I-1-3), (I-1-5), and (I-1-
6), formula (I-1-8), formula (I-1-9), formula (I-1-10), formula (I-1-11) or formula (I-1-12) (provided that Rf is a trifluoromethyl group).

Synthesis of Compound (I) Compound (I) can be prepared, for example, by reacting norbornene (ie, bicyclo [2.
2.1] Hept-2-ene) derivative and the corresponding hydrosilane compound are subjected to a conventional hydrosilylation reaction,
It can be synthesized by reacting in the presence of a hydrosilylation catalyst without solvent or in an appropriate solvent.

[0064]

Embedded image ^{(Wherein, R, R 1, R 2} , Rf, m and n are each in the general formula ^{(I) R, R 1,} R 2, Rf, is synonymous with m and n.)

Examples of the hydrosilylation catalyst include a transition metal catalyst and a radical reaction initiator. Among the hydrosilylation catalysts, examples of the transition metal catalyst include H ₂ PtCl ₆ , K ₂ PtCl ₆ , Na ₂ PtCl ₆ ,
(NH ₄ ) ₂ PtCl ₆ , K ₂ PtCl ₄ , Na ₂ PtCl ₄ , (NH ₄ ) ₂ PtCl ₄ , Pt
Cl ₂ , H ₂ PtBr ₆ , K ₂ PtBr ₆ , Na ₂ PtBr ₆ , PtBr ₄ , K ₂ PtBr
_{4, PtBr 2, K 2 PtI} 6, Na 2 PtI 6, PtI 4, PtI 2, PtCl 2 (C 6
_{H 5 CN), PtCl 2 (} CH 3 CN) 2, PtCl 2 [P (C 6 H 5) 3] 2, cis-PtCl
₂ (styrene) ₂ , cis-PtCl ₂ (p-chlorostyrene) ₂ , KPtC
l ₃ (styrene) ₂ , (n-Bu) ₄ NPtCl ₃ (styrene) ₂ (however, nB
u shows an n-butyl group. The same applies hereinafter. ) And the following formula (iii)
A compound represented by

[0066]

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Trans-PtCl ₂ (NH ₃ ) ₂ , cis-PtCl ₂ [P (C
_{2 H 5) 3) 2,} cis-PtCl 2 [P (n-Bu) 3] 2, [(n-Bu) 4 N] 2 PtCl 6,
[P (C ₆ H ₅ ) ₄ ] ₂ PtCl ₄ , (n-Bu) ₄ NPtI ₃ (CO), [(n-Bu) ₄ N] ₂ -ci
s-PtCl ₂ (SnCl ₃ ) ₂ , [(CH ₃ ) ₄ N] ₃ Pt (SnCl ₃ ) ₅ , [bis (triphenylphosphine) iminium] Pt (SnCl ₃ ) ₃ [As (C ₂ H
₅ ) ₃ ] ₂ , (C ₂ H ₅ ) ₄ NPt (SnCl ₃ ) ₃ (1,5-cyclooctadiene), platinum-activated carbon, platinum catalyst such as platinum black; PdCl
₂ [P (C ₆ H ₅ ) ₃ ] ₂ , palladium catalyst such as PdCl ₂ (1,5-cyclooctadiene), palladium-activated carbon, palladium black; HRh [P (C ₆ H ₅ ) ₃ ] ₄ , rhodium A rhodium catalyst such as activated carbon; an iridium catalyst such as IrCl ₃ ; a ruthenium catalyst such as RuCl ₃ ; a cobalt catalyst such as Co ₂ (CO) ₈ ; NiCl ₂ , NiBr ₂ , Ni
Nickel catalysts such as (CN) ₂ ; CuCl ₂ , CuBr ₂ , CuCl, CuB
r, copper catalysts such as CuCN, and the like.

Among these transition metal catalysts, H ₂ PtCl ₆ ,
_{K 2 PtCl 6, Na 2 PtCl} 6, K 2 PtCl 4, Na 2 PtCl 4, PtCl 2, H 2
_{PtBr 6, K 2 PtBr 6,} Na 2 PtBr 6, K 2 PtBr 4, platinum - platinum catalysts such as activated carbon are preferred. The transition metal catalysts can be used alone or in combination of two or more. Further, the transition metal catalyst may be added after being dissolved in an organic solvent such as i-propyl alcohol. The amount of the transition metal catalyst used is usually 0.00001 to 1,000 parts by weight based on 100 parts by weight of the hydrosilane compound.

Further, as the radical reaction initiator,
For example, benzoyl parkide, lauroyl parkide, diisopropyl peroxydicarbonate, t-
Butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, azobisisobutyronitrile, azobis (2,
4-dimethylvaleronitrile), azobis (4-methoxy-2,4-dimethylvaleronitrile) and the like. These radical reaction initiators can be used alone or in combination of two or more. The amount of the radical reaction initiator to be used is generally 0.01 to 1,000 parts by weight based on 100 parts by weight of the hydrosilane compound.

Examples of the solvent used for the hydrosilylation reaction include aromatic hydrocarbons such as benzene, toluene, and xylene; n-hexane, n-heptane, and n-hexane.
Aliphatic hydrocarbons such as octane; ethers such as benzyl ethyl ether, di-n-hexyl ether and tetrahydrofuran; dichloromethane, chloroform, 1,
Halogenated hydrocarbons such as 2-dichloroethane; 2-butanone, 2-pentanone, 3-methyl-2-butanone,
Linear or branched ketones such as 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone and 2-octanone; Cyclic ketones such as pentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, isophorone; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n -Propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol Propylene glycol monoalkyl ether acetates such as coal mono-sec-butyl ether acetate and propylene glycol mono-t-butyl ether acetate; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, n-propyl 2-hydroxypropionate, I-propyl hydroxypropionate, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate,
Alkyl 2-hydroxypropionates such as sec-butyl 2-hydroxypropionate and t-butyl 2-hydroxypropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Alkyl 3-alkoxypropionates such as ethyl ethoxypropionate;

N-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, 1-octanol, 1-nonanol, benzyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Mono-n-propyl ether,
Ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-
alcohols such as n-propyl ether; dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate; ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate , 2-
Methyl hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, Other esters such as n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N- Dimethylacetamide, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Examples thereof include caproic acid, caprylic acid, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and acetonitrile. These solvents can be used alone or in combination of two or more. The amount of the solvent used is usually 2,000 parts by weight or less based on 100 parts by weight of the hydrosilane compound.

This hydrosilylation reaction is preferably carried out without a solvent or in a solvent such as toluene, xylene, n-hexane, tetrahydrofuran or dichloromethane. Furthermore, this hydrosilylation reaction is preferably performed in a stream of nitrogen or argon under anhydrous conditions.
The temperature of this hydrosilylation reaction is usually -50 to +3
00 ° C., preferably 0-200 ° C., and the reaction time is:
Usually, it is about 5 minutes to 1,000 hours. It is generally considered that the general hydrosilylation reaction is desirably performed under normal pressure or higher pressure. However, in the case of the hydrosilylation reaction for synthesizing the compound (I), the reaction is performed under a pressure lower than normal pressure. The reaction is also possible and has the advantage that no special reaction vessel is required.

In such a hydrosilylation reaction, the compound (I) in which the silicon atom represented by the general formula (I) is bonded to the 2-position of the bicyclo [2.2.1] heptane ring at the highest position is usually used. ) And compound (I) bonded to the 3-position
Are generated at the same time. This mixture can be used as it is, for example, as a raw material for producing a polysiloxane-based resin. If necessary, for example, distillation, recrystallization, liquid chromatography, gas chromatography, etc. I) can be separated.

Use of Compound (I) Compound (I) is extremely useful as a starting material for synthesizing compound (II). Compound (I) in which the total number of halogen atoms and groups OR ² as R ¹ is 2 or 3
Is a Si-halogen atom bond and / or Si-OR
It is also very useful as a raw material for producing an alkali-soluble polysiloxane resin via a hydrolysis reaction of ^two bonds and a polycondensation reaction of silanol groups. This in the production of polysiloxane-based resin, pre-hydrolysis at least part total number 2 or 3, Compound (I) in said halogen atom or a group OR ² in the halogen atom and the group OR ² as R ¹ It can be used after being decomposed and converted to a silanol group, and the compound (III) described later can be copolycondensed. Also, if necessary, R ¹
The total number of halogen and radical OR ² as is 1 Compound (I), and / or the compound compound was converted to silanol groups in advance hydrolyzing halogen atom or a group OR ² in (I) the Can be co-condensed to adjust the molecular weight or molecular structure of the polysiloxane resin. Further, in some cases, other silane compounds having two or more functional groups for the condensation reaction, other monofunctional silane compounds for the condensation reaction, or cyclic polysiloxanes other than the compound (III) can be co-condensed or co-polycondensed.

The alkali-soluble polysiloxane resin thus obtained is, for example, far ultraviolet, ultraviolet,
Radiation-sensitive acid generators (eg, onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, etc.) and alkali-soluble compounds that generate acids upon irradiation with various types of radiation such as charged particle beams and X-rays. Mixing with a control agent (for example, a compound having an acidic functional group such as a phenolic hydroxyl group and a carboxyl group into which one or more substituents capable of dissociating in the presence of an acid have been introduced into the acidic functional group) Thereby, it can be used very suitably as a positive type chemically amplified resist, and by mixing with the radiation-sensitive acid generator, and a compound capable of crosslinking the polysiloxane resin in the presence of an acid, It can be used very suitably as a negative type chemically amplified resist. These positive or negative chemically amplified resists have excellent properties such as dry etching resistance, transparency to radiation, resolution, and developability. Further, compound (I) is a raw material of a polysiloxane resin in another technical field, or another silicon-containing alicyclic compound having a similar norbornane (ie, bicyclo [2.2.1] heptane) ring structure. It is also useful as a raw material or the like.

Compound (II) In the formula (II), R ^{1 is} a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; a halogen atom; Examples of the ^primary , secondary or tertiary amino group include, for example, the monovalent hydrocarbon groups exemplified for R ¹ in the above general formula (I); monovalent halogenated hydrocarbon groups; halogen atoms; ,
Examples include the same groups as the secondary or tertiary amino groups. As R ¹ in the general formula (II),
Methyl group, ethyl group, cyclohexyl group, phenyl group,
A pentafluorophenyl group, a chlorine atom, a dimethylamino group and the like are preferable.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms for R ² ; and the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms include, for example, R 1 in the above-mentioned general formula (I). ^And monovalent hydrocarbon groups exemplified for ² ; and the same groups as the monovalent halogenated hydrocarbon groups. In the formula (i) representing R ² , X is a monovalent hydrocarbon group having 1 to 20 carbon atoms;
Examples of the 20 monovalent halogenated hydrocarbon group include, for example,
Examples include the same monovalent hydrocarbon groups as X in the general formula (I); and the same groups as the monovalent halogenated hydrocarbon groups. R ² in the general formula (II) is particularly preferably a methyl group, an ethyl group, a t-butyl group, a trimethylsilyl group, or the like.

Examples of the monovalent acid dissociable organic group for Z include, for example, a tertiary alkyl group and a group that forms an acetal group together with an oxygen atom to which Z is bonded (hereinafter, referred to as an “acetal-forming group”). ), A substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group (excluding a tertiary alkyl group), a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group, and a cyclic acid-dissociable group. Can be mentioned.

The tertiary alkyl group includes, for example, t
-Butyl group, 1,1-dimethylpropyl group, 1-methyl-1-ethylpropyl group, 1,1-dimethylbutyl group,
1-methyl-1-ethylbutyl group, 1,1-dimethylpentyl group, 1-methyl-1-ethylpentyl group, 1,1
-Dimethylhexyl group, 1,1-dimethylheptyl group,
Examples thereof include a 1,1-dimethyloctyl group.
Examples of the acetal-forming group include a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an i-propoxymethyl group, an n-butoxymethyl group,
t-butoxymethyl group, n-pentyloxymethyl group,
n-hexyloxymethyl group, cyclopentyloxymethyl group, cyclohexyloxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-i-propoxyethyl group, 1-n-butoxy Ethyl group, 1-t-butoxyethyl group, 1-n-pentyloxyethyl group, 1-n-hexyloxyethyl group, 1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, 1-methoxypropyl group, 1 −
Ethoxypropyl group, (cyclohexyl) (methoxy) methyl group, (cyclohexyl) (ethoxy) methyl group, (cyclohexyl) (n-propoxy) methyl group, (cyclohexyl) (i-propoxy) methyl group, (cyclohexyl)
And a (cyclohexyloxy) methyl group.

The substituted methyl group includes, for example, phenacyl group, p-bromophenacyl group, p-methoxyphenacyl group, p-methylthiophenacyl group, α-
Methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, p
-Bromobenzyl group, p-nitrobenzyl group, p-methoxybenzyl group, p-methylthiobenzyl group, p-ethoxybenzyl group, p-ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n -Propoxycarbonylmethyl group, i-
Examples thereof include a propoxycarbonylmethyl group, an n-butoxycarbonylmethyl group, and a t-butoxycarbonylmethyl group. Examples of the 1-substituted ethyl group include a 1-cyclopropylethyl group, a 1-phenylethyl group, a 1,1-diphenylethyl group, a 1-methoxycarbonylethyl group, a 1-ethoxycarbonylethyl group, n-propoxycarbonylethyl group, 1-i-
Examples thereof include a propoxycarbonylethyl group, a 1-n-butoxycarbonylethyl group, and a 1-t-butoxycarbonylethyl group.

The 1-branched alkyl group includes
For example, an i-propyl group, a sec-butyl group, a 1-methylbutyl group and the like can be mentioned. Examples of the silyl group include trimethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triethylsilyl, i-propyldimethylsilyl, and methyldi-i.
-Propylsilyl group, tri-i-propylsilyl group, t
-Butyldimethylsilyl group, methyldi-t-butylsilyl group, tri-t-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilyl group, triphenylsilyl group and the like. Examples of the germyl group include a trimethylgermyl group, an ethyldimethylgermyl group, a methyldiethylgermyl group, a triethylgermyl group, an i-propyldimethylgermyl group, a methyldi-i-propylgermyl group, and a trimethylgermyl group. -I-propylgermyl group, t-butyldimethylgermyl group, methyldi-t
-Butylgermyl group, tri-t-butylgermyl group, phenyldimethylgermyl group, methyldiphenylgermyl group, triphenylgermyl group and the like.
Further, as the alkoxycarbonyl group, for example,
Examples include a methoxycarbonyl group, an ethoxycarbonyl group, an i-propoxycarbonyl group, and a t-butoxycarbonyl group.

Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a heptanoyl group, a hexanoyl group, a valeryl group, a pivaloyl group, an isovaleryl group, a lauryloyl group, a myristoyl group, a palmitoyl group, a stearoyl group, and an oxalyl group. Group, malonyl group, succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoil group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group,
Fumaroyl group, mesaconoyl group, camphoroyl group, benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, floyl group, tenoyl group, nicotinoyl group, isonicotinoyl group , P-toluenesulfonyl group, mesyl group and the like. Further, examples of the cyclic acid dissociable group include a 3-oxocyclohexyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, a tetrahydrothiofuranyl group, a 3-bromotetrahydropyranyl group, -Methoxytetrahydropyranyl group, 2-oxo-4-methyl-4-tetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group,
Examples thereof include a 3-tetrahydrothiophene-1,1-dioxide group.

Among these acid dissociable organic groups, t-butyl, t-butoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, methoxymethyl,
Acetal-forming groups such as an ethoxymethyl group, a 1-methoxyethyl group and a 1-ethoxyethyl group are preferred.

As R in the general formula (II), both a hydrogen atom and a methyl group are preferable. The general formula (I
Rf in I) is preferably a hydrogen atom, a methyl group or a trifluoromethyl group. Further, m and n in the general formula (II) are, in particular,
0 or 1 is preferred.

Preferred specific examples of compound (II) include:
Formulas (I-1-1) to (I-1-36) and Formulas (I-2-1) to (I-2)
-44), Formulas (I-3-1) to (I-3-4), Formulas (I-4-1) to (I
-4-4) wherein a hydrogen atom of a hydroxyl group in a compound represented by the formula (where Rf is a hydrogen atom) is a t-butyl group,
t-butoxycarbonyl group, tetrahydropyranyl group,
Compounds substituted with a tetrahydrofuranyl group, a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group or a 1-ethoxyethyl group; the compounds of the above formulas (I-1-1) to (I-1-3)
6), Formulas (I-2-1) to (I-2-44), Formulas (I-3-1) to (I-3)
-4), the hydrogen atom of the hydroxyl group in the compounds represented by the formulas (I-4-1) to (I-4-4) (where Rf is a methyl group) is replaced by a t-butyl group. , T-butoxycarbonyl group,
Compounds substituted with a tetrahydropyranyl group, a tetrahydrofuranyl group, a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group or a 1-ethoxyethyl group; the above formulas (I-1-1) to (I-1-36) , Formulas (I-2-1) to (I-2-4)
4), Formulas (I-3-1) to (I-3-4), Formulas (I-4-1) to (I-4)
-4) wherein Rf is a trifluoromethyl group, and a hydrogen atom of a hydroxyl group is represented by t-
Butyl group, t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group or 1
And compounds substituted with an ethoxyethyl group.

Among these compounds (II), the compounds represented by the formulas (I-1-2), (I-1-3), (I-1-5) and (I-1-
6), formula (I-1-8), formula (I-1-9), formula (I-1-10), formula (I-1-11) or formula (I-1-12) (provided that Rf is a trifluoromethyl group.) A hydrogen atom of a hydroxyl group in the compound represented by the formula (1) is replaced with a t-butyl group, a t-butoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a methoxymethyl group, an ethoxy group. Compounds substituted with a methyl group, a 1-methoxyethyl group or a 1-ethoxyethyl group are preferred.

Compound (II) can be synthesized , for example, by reacting a norbornene derivative represented by the general formula (VI) with a corresponding hydrosilane compound as shown in the following formula.
Method for hydrosilylation reaction in the same manner as in the method for synthesizing compound (I)

[0088]

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(Wherein R, R ¹ , R ² , Rf, Z, m and n are each R, R ¹ ,
It has the same meaning as R ² , Rf, Z, m and n. The compound can be synthesized by a method in which a hydrogen atom of a hydroxyl group in compound (I) is replaced with a monovalent acid-dissociable organic group.

The above method is more specifically described as follows. (A) When Z is a t-butoxycarbonyl group, the hydroxyl group in the compound (I) is converted into a compound in the presence of a catalytic amount of 4-dimethylaminopyridine. (B) When Z is a tetrahydropyranyl group, the hydroxyl group in the compound (I) is converted into 2,3-dihydro-4H-pyran by a conventional method. (C) When Z is an acetal-forming group such as a 1-alkoxyethyl group, the addition reaction of the hydroxyl group in the compound (I) with the corresponding alkyl vinyl ether is carried out by a conventional method. can do. Each of the reactions (a) to (c) can be carried out without a solvent or in an appropriate solvent. Examples of the solvent in these cases include the same solvents as those exemplified in the synthesis of the compound (I). In addition, reaction conditions such as reaction temperature and reaction time are appropriately selected according to each method, reagents to be reacted with compound (I), and the like. In particular, according to the method (a), the compound (II) can be efficiently synthesized.
On the other hand, a sodium hydride catalyst generally used for replacing a hydrogen atom of a hydroxyl group in a general organic compound with a t-butoxycarbonyl group can synthesize the compound (II) from the compound (I). Have difficulty.

[0091] Compound (II) Total number of compounds which are 2 or 3 halogen atoms and groups OR ² as application R ¹ of (II) is, Si- halogen atom bond and / or Si-OR ² bond hydrolysis It is extremely useful as a raw material for producing a polysiloxane resin having an acid-dissociable organic group via a decomposition reaction and a polycondensation reaction of silanol groups. When producing this polysiloxane resin, a halogen atom as R ¹ and a group OR ²
And at least part of the halogen atom or the group OR ² in the compound (II) having a total number of 2 or 3 can be hydrolyzed in advance to be converted to a silanol group and used. IV). Further, if necessary, the compound (II) in which the total number of the halogen atom as R ¹ and the group OR ² is 1 and / or the halogen atom or the group OR ² in the compound (II) is hydrolyzed in advance. The compound converted to a silanol group can be co-condensed to adjust the molecular weight or molecular structure of the polysiloxane resin. further,
In some cases, other silane compounds having two or more functions with respect to the condensation reaction or other silane compounds having a single function with respect to the condensation reaction can be co-condensed or co-polycondensed.

The polysiloxane resin having an acid-dissociable organic group obtained in this manner has an affinity for an alkaline aqueous solution by dissociating the acid-dissociable organic group in the presence of an acid to form a hydroxyl group. Is growing,
For example, radiation-sensitive acid generators (eg, onium salt compounds, halogen-containing compounds, and the like) that generate acids by irradiation with various radiations such as far ultraviolet rays, ultraviolet rays, charged particle beams, and X-rays.
Diazoketone compound, sulfone compound, sulfonic acid compound, etc.)
It can be very suitably used as a positive chemically amplified resist excellent in transparency to radiation, resolution, developability and the like. Further, the compound (II) is useful as a raw material for polysiloxane resins in other technical fields and as a raw material for other silicon-containing alicyclic compounds having the same norbornane ring structure.

Compound (III) In the general formula (III), Y is a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; a halogen atom and a secondary or Examples of the tertiary amino group include the monovalent hydrocarbon groups exemplified for R ¹ in the formula (I); monovalent halogenated hydrocarbon groups; halogen atoms and secondary or tertiary amino groups. And the same groups as described above. Of these groups, the monovalent hydrocarbon group is preferably a methyl group, an ethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, an adamantyl group, or the like, and is preferably a monovalent halogenated hydrocarbon group. Are preferably a trifluoromethyl group, a pentafluoroethyl group, a pentafluorophenyl group and the like, a halogen atom is preferably a chlorine atom, and an amino group is preferably a dimethylamino group.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms and the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms of R ² in Y include, for example, R 1 in the above-mentioned general formula (I). ^{The same} groups as the monovalent hydrocarbon group and the monovalent halogenated hydrocarbon group exemplified for ² can be exemplified. Of these groups, monovalent hydrocarbon groups include methyl, ethyl, n-propyl, i-
A propyl group and the like are preferable, and a monovalent halogenated hydrocarbon group is preferably a trifluoromethyl group and a pentafluoroethyl group.

In the formula (i) representing R ² , X represents a monovalent hydrocarbon group having 1 to 20 carbon atoms and a monovalent hydrocarbon group having 1 to 2 carbon atoms.
Examples of the monovalent halogenated hydrocarbon group of 0 include, for example, the monovalent hydrocarbon groups and the same groups as the monovalent halogenated hydrocarbon groups exemplified for R ² in the formula (I). be able to. Of these groups,
As the monovalent hydrocarbon group, a methyl group, an ethyl group, a phenyl group and the like are preferable, and as the monovalent halogenated hydrocarbon group, a trifluoromethyl group and a pentafluoroethyl group are preferable.

Examples of the linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms of X include, for example, the same groups as the alkoxyl groups exemplified for X in the above general formula (I). Can be. Among these alkoxyl groups, a methoxy group, an ethoxy group and the like are preferable. X in the formula (i) is particularly preferably a methyl group, a phenyl group, a methoxy group or the like. Further, a in formula (i) is particularly preferably 1 to 4.

As Y in the general formula (III),
Methyl, phenyl, trifluoromethyl, pentafluorophenyl, chlorine, dimethylamino, methoxy, ethoxy and the like are preferred. The general formula (II
As R in I), both a hydrogen atom and a methyl group are preferred. Rf in the general formula (III) is preferably a hydrogen atom, a methyl group or a trifluoromethyl group. Further, p in the general formula (III) is particularly preferably 3 to 5, and n in the general formula (III) is particularly preferably 0 or 1.

Preferred specific examples of compound (III) include:
Compounds represented by the following formulas (III-1-1) to (III-1-6) and formulas (III-2-1) to (III-2-6) can be exemplified.

[0099]

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[0100]

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[0101]

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[0102]

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[0103] Synthesis of Compound (III) (III) is, for example, as shown in the following formula, a norbornene derivative represented by formula (V), and a corresponding hydrosilane compound,
Method for hydrosilylation reaction in the same manner as in the method for synthesizing compound (I)

[0104]

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(Wherein R, Y, Rf, Z, p and n have the same meanings as R, Y, Rf, Z, p and n in formula (III), respectively); Halogen atom as R ¹ (I) having a total number of 2 or 3 and a group OR ² and / or a compound having a silanol group introduced by hydrolyzing at least a part of a halogen atom or the group OR ² of the compound (I). It can be synthesized by a conventional method, for example, by condensing in a suitable solvent in the presence of an alkaline catalyst or an acidic catalyst. Examples of the solvent used in the above method include the same solvents as those exemplified in the synthesis of the compound (I). In addition, reaction conditions such as reaction temperature and reaction time are appropriately selected according to each method, reagents to be reacted with compound (I), and the like. In the condensation reaction in the above method, two or more kinds of compounds (III) having different p indicating the degree of condensation are produced simultaneously, or the compound (III)
Other compounds (that is, compounds having p less than 3 or more than 10) may be produced as by-products. In the former case, the separation into individual compounds and the composition adjustment of a mixture of two or more compounds (III) can be appropriately performed depending on the use of the compound (III). In the latter case, compound (III)
Separation from a compound other than the compound (III) and adjustment of the content of the compound other than the compound (III) can be appropriately performed depending on the use of the compound (III).

Uses of Compound (III) Compound (III) is extremely useful as a raw material for synthesizing compound (IV). Compound (III) is also extremely useful as a raw material for producing an alkali-soluble polysiloxane resin by a ring-opening polyaddition reaction of the cyclic polysiloxane bond. In producing the polysiloxane resin, the compound (I) in which the total number of the halogen atom as R ¹ and the group OR ² is 2 or 3 and / or the halogen atom or the group OR ^{2 in the} compound (I).
Can be co-polycondensed with a compound in which at least a part of the compound has been converted into a silanol group by hydrolysis in advance. Further, if necessary, the compound (I) in which the total number of the halogen atom as R ¹ and the group OR ² is 1 and / or the halogen atom or the group OR ² in the compound (I) is hydrolyzed in advance. The compound converted to a silanol group can be co-condensed to adjust the molecular weight or molecular structure of the polysiloxane resin. Furthermore, depending on the case, another cyclic polysiloxane, another silane compound having two or more functional groups for the condensation reaction, or another monofunctional silane compound for the condensation reaction can be co-condensed or co-polycondensed.

The alkali-soluble polysiloxane resin thus obtained is, for example, far ultraviolet, ultraviolet,
Radiation-sensitive acid generators (eg, onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, etc.) and alkali-soluble compounds that generate acids upon irradiation with various types of radiation such as charged particle beams and X-rays. Mixing with a control agent (for example, a compound having an acidic functional group such as a phenolic hydroxyl group and a carboxyl group into which one or more substituents capable of dissociating in the presence of an acid have been introduced into the acidic functional group) Thereby, it can be used very suitably as a positive type chemically amplified resist, and by mixing with the radiation-sensitive acid generator, and a compound capable of crosslinking the polysiloxane resin in the presence of an acid, It can be used very suitably as a negative type chemically amplified resist. These positive or negative chemically amplified resists have excellent properties such as dry etching resistance, transparency to radiation, resolution, and developability. Further, the compound (III) is also useful as a raw material for polysiloxane resins in other technical fields and as a raw material for other silicon-containing alicyclic compounds having the same norbornane ring structure.

Compound (IV) In the general formula (IV), Y is a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; a halogen atom and a secondary or Examples of the tertiary amino group include the monovalent hydrocarbon groups exemplified for R ¹ in the formula (I); monovalent halogenated hydrocarbon groups; halogen atoms and secondary or tertiary amino groups. And the same groups as described above. Of these groups, the monovalent hydrocarbon group is preferably a methyl group, an ethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, an adamantyl group, or the like, and is preferably a monovalent halogenated hydrocarbon group. Are preferably a trifluoromethyl group, a pentafluoroethyl group, a pentafluorophenyl group and the like, a halogen atom is preferably a chlorine atom, and an amino group is preferably a dimethylamino group.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms and the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms of R ² in Y include, for example, R 1 in the above-mentioned general formula (I). ^{The same} groups as the monovalent hydrocarbon group and the monovalent halogenated hydrocarbon group exemplified for ² can be exemplified. Of these groups, monovalent hydrocarbon groups include methyl, ethyl, n-propyl, i-
A propyl group and the like are preferable, and a monovalent halogenated hydrocarbon group is preferably a trifluoromethyl group and a pentafluoroethyl group.

In the formula (i) representing R ² , X is a monovalent hydrocarbon group having 1 to 20 carbon atoms and a monovalent hydrocarbon group having 1 to 2 carbon atoms.
Examples of the monovalent halogenated hydrocarbon group of 0 include, for example, the monovalent hydrocarbon groups and the same groups as the monovalent halogenated hydrocarbon groups exemplified for R ² in the formula (I). be able to. Of these groups,
As the monovalent hydrocarbon group, a methyl group, an ethyl group, a phenyl group and the like are preferable, and as the monovalent halogenated hydrocarbon group, a trifluoromethyl group and a pentafluoroethyl group are preferable.

Examples of the linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms for X include, for example, the same groups as the alkoxyl groups exemplified for X in the above general formula (I). Can be. Among these alkoxyl groups, a methoxy group, an ethoxy group and the like are preferable. X in the formula (i) is particularly preferably a methyl group, a phenyl group, a methoxy group or the like. Further, a in formula (i) is particularly preferably 1 to 4.

As Y in the general formula (IV),
Methyl, phenyl, trifluoromethyl, pentafluorophenyl, chlorine, dimethylamino, methoxy, ethoxy and the like are preferred.

Examples of the monovalent acid dissociable organic group for Z include the same groups as the monovalent acid dissociable organic groups exemplified for Z in formula (II). Among these acid dissociable organic groups, t-butyl group, t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group And the like are preferred.

As R in the general formula (IV), both a hydrogen atom and a methyl group are preferable. The general formula (I
Rf in V) is preferably a hydrogen atom, a methyl group or a trifluoromethyl group. Further, p in the general formula (IV) is particularly preferably 3 to 5, and n in the general formula (IV) is particularly preferably 0 or 1.

Preferred specific examples of compound (IV) include:
In the compounds represented by the formulas (III-1-1) to (III-1-6) and the formulas (III-2-1) to (III-2-6), a hydrogen atom of a hydroxyl group is represented by
Examples thereof include compounds substituted with a t-butyl group, a t-butoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, or a 1-ethoxyethyl group.

Among these compounds (IV), in particular, the compounds represented by the formula (III-1-3), the formula (III-1-6), the formula (III-2-3) or the formula (III-2-3)
The hydrogen atom of the hydroxyl group in the compound represented by I-2-6) is represented by t-
Butyl group, t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group or 1
-A compound substituted with an ethoxyethyl group is preferred.

[0117] Synthesis of Compound (IV) (IV) is, for example, as shown in the following formula, a norbornene derivative represented by the general formula (VI), and corresponding hydrosilane compound,
Method for hydrosilylation reaction in the same manner as in the method for synthesizing compound (I)

[0118]

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(Wherein R, Y, Rf, Z, p and n have the same meanings as R, Y, Rf, Z, p and n in formula (IV), respectively); Halogen atom as R ¹ (II) in which the total number of the group and the group OR ² is 2 or 3, and / or a compound obtained by hydrolyzing at least a part of the halogen atom or the group OR ² of the compound (II) to introduce a silanol group. By a conventional method in the presence of an alkaline catalyst or an acidic catalyst in a suitable solvent; a method of substituting a hydrogen atom of a hydroxyl group in compound (III) with a monovalent acid dissociable organic group. can do. Examples of the solvent used in the above method include the same solvents as those exemplified in the synthesis of the compound (II). The reaction conditions such as the reaction temperature and the reaction time are appropriately selected according to each method, the reagent to be reacted with the compound (II), and the like.
In the condensation reaction in the above method, two or more kinds of compounds (IV) having different ps representing the degree of condensation are simultaneously produced, or a compound other than the compound (IV) (that is, p is less than 3 or more than 10). Compound) may also be by-produced. In the former case, the separation into individual compounds and the adjustment of the composition of a mixture of two or more compounds (IV) can be performed by the compound (I
It can be carried out appropriately according to the use of V). In the latter case, the separation of the compound (IV) from other compounds and the adjustment of the content of the compound other than the compound (IV) can be appropriately performed depending on the use of the compound (IV).

More specifically, the above-mentioned method can be carried out, for example, in the following manner: (a) when Z is a t-butoxycarbonyl group, the hydroxyl group in the compound (III) is converted into a compound in the presence of a catalytic amount of 4-dimethylaminopyridine; (B) when Z is a tetrahydropyranyl group, the hydroxyl group in the compound (III) is converted to 2,3-dihydro-4H-pyran by a conventional method. (C) When Z is an acetal-forming group such as a 1-alkoxyethyl group, the addition reaction of the hydroxyl group in the compound (III) with the corresponding alkyl vinyl ether is carried out by a conventional method. can do. Each of the reactions (a) to (c) can be carried out without a solvent or in an appropriate solvent. Examples of the solvent in these cases include the same solvents as those exemplified in the synthesis of the compound (I). In addition, reaction conditions such as reaction temperature and reaction time are appropriately selected according to each method, reagents to be reacted with compound (III), and the like. In particular, according to the method (a), the compound (IV) can be efficiently synthesized.
On the other hand, a sodium hydride catalyst generally used for replacing a hydrogen atom of a hydroxyl group in a general organic compound with a t-butoxycarbonyl group can synthesize the compound (IV) from the compound (III). Have difficulty.

Use of Compound (IV) Compound (IV) is extremely useful as a raw material for producing a polysiloxane resin having an acid-dissociable organic group by a ring-opening polyaddition reaction of its cyclic polysiloxane bond. . When producing this polysiloxane resin, R ¹
(II) and / or the compound (II) in which the total number of the halogen atom and the group OR ² is 2 or 3
A compound in which at least a part of the halogen atom or the group OR ² therein has been hydrolyzed in advance and converted to a silanol group can be copolycondensed. If necessary, the compound (II) in which the total number of the halogen atom as R ¹ and the group OR ² is 1 and / or the halogen atom or the group OR ² in the compound (II) is hydrolyzed in advance. The compound converted to a silanol group can be co-condensed to adjust the molecular weight or molecular structure of the polysiloxane resin. Further, optionally, other cyclic polysiloxanes,
Other silane compounds having two or more functions with respect to the condensation reaction or other monofunctional silane compounds with respect to the condensation reaction can be co-condensed or co-polycondensed.

The polysiloxane resin having an acid-dissociable organic group obtained as described above has an affinity for an alkaline aqueous solution because the acid-dissociable organic group dissociates in the presence of an acid to form a hydroxyl group. Is growing,
For example, radiation-sensitive acid generators (eg, onium salt compounds, halogen-containing compounds, and the like) that generate acids by irradiation with various radiations such as far ultraviolet rays, ultraviolet rays, charged particle beams, and X-rays.
Diazoketone compound, sulfone compound, sulfonic acid compound, etc.)
It can be very suitably used as a positive chemically amplified resist excellent in transparency to radiation, resolution, developability and the like. Further, the compound (IV) is also useful as a raw material for polysiloxane resins in other technical fields and as a raw material for other silicon-containing alicyclic compounds having a similar norbornane ring structure.

[0123]

Embodiments of the present invention will be described below more specifically with reference to examples. However, the present invention is not limited to these embodiments.

EXAMPLE 1 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 13.4 g of trimethoxysilane and 5- [2-hydroxy-2,2-di (trifluoromethyl)] were added. Add 20.0 g of bicyclo [2.2.1] hept-2-ene,
After stirring at room temperature, 0.2 ml of chloroplatinic acid (H ₂ PtCl ₆ ) was added.
The reaction was started by adding 0.2 ml of a molar i-propyl alcohol solution, and the mixture was heated and refluxed at 100 ° C. for 48 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered with suction on celite, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, the crude product was
Purification was performed by distillation under reduced pressure at mmHg and 110 ° C. to obtain 12.2 g of a compound.

About this compound, ¹ H-NMR spectrum (chemical shift “σH”), ¹³ C-NMR spectrum (chemical shift “σC”), ²⁹ Si-NMR spectrum (chemical shift “σSi”), ¹⁹ F-NMR When the spectrum (chemical shift “σF”), infrared absorption spectrum (IR), and mass spectrum (FABMS) were measured, the measured values were as follows, and the above formula (I-1-3) (where Rf was (It is a trifluoromethyl group.) This compound (I) was a mixture of a compound in which a trimethoxysilyl group was bonded to the 2-position of the bicyclo [2.2.1] heptane ring and a compound in which the compound was bonded to the 3-position of the bicyclo [2.2.1] heptane ring. . σH: 3.6 ppm (methoxy group). σC: 123 ppm (trifluoromethyl group), 51
ppm (methoxy group). σSi: -45 ppm. ? F: -76 to -79 ppm. IR: 3400 cm ^-1 (hydroxyl group), 2847 cm
^-1 (methoxy group), 1217 cm ^-1 (CF bond), 1
097 cm ^-1 (siloxane group). FABMS: m / z = 397 (M ⁺⁺ 1).

Example 2 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 38.8 g of triethoxysilane and 5- [2-hydroxy-2,2-di (trifluoromethyl)] bicyclo were added. [2.2.1] hept-2-ene 43.2 g was added,
After stirring at room temperature, 0.2 ml of chloroplatinic acid (H ₂ PtCl ₆ ) was added.
The reaction was started by adding 0.1 ml of a molar i-propyl alcohol solution, and the mixture was heated and refluxed at 100 ° C. for 30 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered with suction on celite, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, the crude product was
Purification was performed by distillation under reduced pressure at mmHg and 105 ° C. to obtain 59.8 g of a compound.

About this compound, ¹ H-NMR spectrum (chemical shift “σH”), ¹³ C-NMR spectrum (chemical shift “σC”), ²⁹ Si-NMR spectrum (chemical shift “σSi”), ¹⁹ F-NMR When the spectrum (chemical shift “σF”), infrared absorption spectrum (IR), and mass spectrum (FABMS) were measured, the measured values were as follows, and the above formula (I-1-6) (where Rf was (It is a trifluoromethyl group.) This compound (I) was a mixture of substantially equal amounts of a compound having a triethoxysilyl group bonded to the 2-position of the bicyclo [2.2.1] heptane ring and a compound having the triethoxysilyl group bonded to the 3-position. . σH: 3.8 ppm (ethoxy group), 1.2 ppm
(Ethoxy group). σC: 123 ppm (trifluoromethyl group), 59
ppm (ethoxy group), 18 ppm (methyl group). σSi: -48 ppm. ? F: -76 to -79 ppm. IR: 3400 cm ^-1 (hydroxyl group), 2878 cm
^-1 (methoxy group), 1215 cm ^-1 (CF bond), 1
082 cm ^-1 (siloxane group). FABMS: m / z = 439 (M ⁺⁺ 1).

Example 3 To a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 3.0 g of the compound (I) obtained in Example 2 and 10 ml of tetrahydrofuran were added, and the mixture was cooled with ice in a nitrogen stream. When the temperature of the reaction solution reached 5 ° C or lower, 16.7 mg of 4-dimethylaminopyridine was added, and then a solution of 1.64 g of di-t-butyl dicarbonate dissolved in 5 ml of tetrahydrofuran Was added dropwise over 15 minutes. After stirring for 1 hour after the completion of the dropwise addition, the reaction solution was returned to room temperature and further stirred for 5 hours. afterwards,
After adding 50 ml of n-hexane to the reaction solution and transferring it to a separating funnel, the organic layer was washed three times with ice water. Thereafter, the organic layer was poured into a beaker, dried over anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain a crude product. Thereafter, the crude product was subjected to silica gel chromatography, and from the n-hexane fraction, Compound 3.
5 g were obtained.

About this compound, ¹ H-NMR spectrum (chemical shift “σH”), ¹³ C-NMR spectrum (chemical shift “σC”), ²⁹ Si-NMR spectrum (chemical shift “σSi”), ¹⁹ F-NMR When the spectrum (chemical shift “σF”), infrared absorption spectrum (IR), and mass spectrum (FABMS) were measured, the measured values were as follows, and the above formula (I-1-6) (where Rf was The compound (I) was identified as a compound in which a hydrogen atom of a hydroxyl group in the compound (I) was replaced with a t-butoxycarbonyl group. σH: 3.8 ppm (ethoxy group), 1.2 ppm
(Ethoxy group), 1.5 ppm (t-butyl group). σC: 149 ppm (carbonate group), 122 pp
m (trifluoromethyl group), 85 ppm (t-butoxy group), 59 ppm (ethoxy group), 28 ppm (t-
Butyl group), 18 ppm (methyl group). σSi: -48 ppm. ? F: -72.7 to -73.3 ppm. IR: 3400 cm ^-1 (hydroxyl group), 2879 cm
^-1 (methoxy group), 1774 cm ^-1 (carbonate group), 1221 cm ^-1 (CF bond), 1082 cm ^-1
(Siloxane group). FABMS: m / z = 539 (M ⁺⁺ 1).

Example 4 To a three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 10 g of the compound (I) obtained in Example 1 and 50 ml of tetrahydrofuran were added, and the mixture was stirred in a nitrogen stream under ice-cooling. Then, when the temperature of the reaction solution reached 5 ° C. or less, 48.4 mg of 4-dimethylaminopyridine was added, and then a solution obtained by dissolving 4.75 g of di-tert-butyl dicarbonate in 10 ml of tetrahydrofuran was added.
It was added dropwise over a period of minutes. After stirring for 1 hour after dropping,
The reaction solution was returned to room temperature and stirred for another 5 hours. Thereafter, 100 ml of n-hexane was added to the reaction solution, and the mixture was transferred to a separating funnel. The organic layer was washed three times with ice water. Thereafter, the organic layer was poured into a beaker, dried over anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain 10.3 g of a compound. For this compound, ¹
When the H-NMR spectrum (chemical shift “σH”) and infrared absorption spectrum (IR) were measured, the measured values were as follows, and the above formula (I-1-3) (where Rf is trifluoromethyl Is identified as Compound (II) in which the hydrogen atom of the hydroxyl group in the compound represented by the formula (II) is substituted with a t-butoxycarbonyl group. σH: 3.8 ppm (ethoxy group), 1.5 ppm
(T-butoxycarbonyl group), 1.2 ppm (ethoxy group). IR: 1770 cm ^-1 (carbonate group), 1220
cm ^-1 (C-F bond), 1098cm ^-1 (siloxane group).

Example 5 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 18.1 g of triethoxysilane and 8- [2-hydroxy-2,2-di (trifluoromethyl)] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (25.0 g) was added, and the mixture was stirred at room temperature. Then, 0.2 ml of a 0.2 mol i-propyl alcohol solution of chloroplatinic acid (H ₂ PtCl ₆ ) was added thereto. The reaction is started and 150
The mixture was heated under reflux at 70 ° C. for 70 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered with suction on celite, and the solvent was distilled off under reduced pressure to obtain a crude product.
Thereafter, the crude product was subjected to silica gel column chromatography, and from the n-hexane fraction, 19.4 g of the compound was obtained.
Obtained. About this compound, ¹ H-NMR spectrum (chemical shift “σH”), infrared absorption spectrum (IR)
Was measured, and the measured values were as follows. The compound was identified as the compound (I) represented by the formula (I-2-6) (where Rf is a trifluoromethyl group). σH: 3.8 ppm (ethoxy group), 1.2 ppm
(Ethoxy group). IR: 3400 cm ^-1 (hydroxyl group), 1220 cm
^-1 (CF bond), 1098 cm ^-1 (siloxane group).

Example 6 To a three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 3 g of the compound (I) obtained in Example 5 and 10 ml of tetrahydrofuran were added, and the mixture was stirred in a nitrogen stream under ice-cooling. When the temperature of the reaction solution reaches 5 ° C. or less,
After adding 4.5 mg of 4-dimethylaminopyridine,
A solution of 1.43 g of di-t-butyl dicarbonate in 5 ml of tetrahydrofuran was added dropwise over 15 minutes. After stirring for 1 hour after the completion of the dropwise addition, the reaction solution was returned to room temperature and further stirred for 5 hours. Thereafter, 50 ml of n-hexane was added to the reaction solution, and the mixture was transferred to a separating funnel. The organic layer was washed three times with ice water. afterwards,
The organic layer was poured into a beaker, dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain a crude product. Thereafter, the crude product was subjected to silica gel column chromatography, and from the n-hexane fraction, compound 3.
2 g were obtained. About this compound, ¹ H-NMR spectrum (chemical shift “σH”), infrared absorption spectrum (I
When R) was measured, the measured values were as follows, and the hydrogen atom of the hydroxyl group in the compound represented by the formula (I-2-6) (where Rf is a trifluoromethyl group) was , T
-Compound (II) substituted with a butoxycarbonyl group was identified. σH: 3.8 ppm (ethoxy group), 1.5 ppm
(T-butoxycarbonyl group), 1.2 ppm (ethoxy group). IR: 1771 cm ^-1 (carbonate group), 1218
cm ^-1 (C-F bond), 1098cm ^-1 (siloxane group).

Example 7 A three-necked flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 12.0 g of methylhydrocyclosiloxane and 52.0 g of methylhydrocyclosiloxane.
-[2-hydroxy-2,2-di (trifluoromethyl)] bicyclo [2.2.1] hept-2-ene 54.
After stirring at room temperature, 8 g of chloroplatinic acid (H ₂ Pt
The reaction was initiated by the addition of 5.0 ml of a 0.2 molar solution of Cl ₆ ) in i-propyl alcohol,
The mixture was refluxed for 0 hours. Then, return the reaction solution to room temperature,
After dilution with n-hexane, suction filtration was performed on celite, and the solvent was distilled off under reduced pressure to obtain 66.0 g of a compound. When this compound was measured for ¹ H-NMR spectrum (chemical shift “σH”) and infrared absorption spectrum (IR), the measured values were as follows, and the above formula (III-1-3) (provided that —Si (CH ₃ ) O—the number of units is 4.). σH: 0.2 ppm (SiCH ₃ group). IR: 3400 cm ^-1 (hydroxyl group), 2847 cm
^-1 (methoxy group), 1218 cm ^-1 (CF bond), 1
098 cm ^-1 (siloxane group).

Example 8 To a three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 5 g of the compound (III) obtained in Example 7 and 15 ml of tetrahydrofuran were added, and the mixture was stirred in a nitrogen stream under ice cooling. When the temperature of the reaction solution reaches 5 ° C. or less,
After adding 36.6 mg of 4-dimethylaminopyridine, a solution of 3.6 g of di-tert-butyl dicarbonate in 5 ml of tetrahydrofuran was added dropwise over 15 minutes. After stirring for 1 hour after the completion of the dropwise addition, the reaction vessel was returned to room temperature and further stirred for 5 hours. Thereafter, 70 ml of n-hexane was added to the reaction solution, and the mixture was transferred to a separating funnel. The organic layer was washed three times with ice water. Thereafter, the organic layer was poured into a beaker, dried over anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain 5.5 g of a compound. The ¹ H-NMR spectrum (chemical shift “σH”) of this compound was measured and found to be as follows. The compound was represented by the above formula (III-1-3) (provided that -Si
The number of (CH ₃ ) O- units is 4. ) Was identified as compound (IV) in which the hydrogen atom of the hydroxyl group in the compound was replaced with a t-butoxycarbonyl group. σH: 1.5 ppm (t-butoxycarbonyl group),
0.2 ppm (SiCH ₃ groups).

Example 9 A three-necked flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 10.0 g of methylhydrocyclosiloxane and 8 g of methylhydrocyclosiloxane.
-[2-hydroxy-2,2-di (trifluoromethyl)] tetracyclo [4.4.0.1 ^2,5 . After adding 56.7 g of [ ^7,10 ] dodec-3-ene and stirring at room temperature, 5.0 ml of a 0.2 mol i-propyl alcohol solution of chloroplatinic acid (H ₂ PtCl ₆ ) was added. The reaction was started and heated at 150 ° C. for 100 hours under reflux. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, suction-filtered on celite, and the solvent was distilled off under reduced pressure to obtain 65.4 g of a compound. For this compound, ¹ H-N
When the MR spectrum (chemical shift “σH”) and the infrared absorption spectrum (IR) were measured, the measured values were as follows, and the above formula (III-2-3) (provided that —Si (CH ₃ ) O
The number of units is 4; ) Was identified as Compound (III). σH: 0.2 ppm (SiCH ₃ group). IR: 3400 cm ^-1 (hydroxyl group), 2849 cm
^-1 (methoxy group), 1220 cm ^-1 (CF bond), 1
100 cm ^-1 (siloxane group).

Example 10 To a three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 5.0 g of the compound (III) obtained in Example 9 and 15 ml of tetrahydrofuran were added, and the mixture was cooled in a nitrogen stream under ice-cooling. When the temperature of the reaction solution reaches 5 ° C. or less, 30.5 mg of 4-dimethylaminopyridine is added, and a solution of 3.0 g of di-tert-butyl dicarbonate dissolved in 5 ml of tetrahydrofuran is added. It was added dropwise over 15 minutes. After stirring for 1 hour after the completion of the dropwise addition, the reaction solution was returned to room temperature, and further stirred at room temperature for 5 hours. Thereafter, 70 ml of n-hexane was added to the reaction solution, transferred to a separating funnel, and the organic layer was washed three times with ice water. Thereafter, the organic layer was poured into a beaker, dried over anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain 5.3 g of a compound. When the ¹ H-NMR spectrum (chemical shift “σH”) of this compound was measured, the measured values were as follows, and the formula (III-2-3) (provided that
The number of —Si (CH ₃ ) O— units is 4. ) Was identified as compound (IV) in which the hydrogen atom of the hydroxyl group in the compound was replaced with a t-butoxycarbonyl group. σH: 1.5 ppm (t-butoxycarbonyl group),
0.2 ppm (SiCH ₃ groups).

Example 11 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 13.8 g of diethoxymethylsilane and 5-
After adding 40 g of (2,2,2-trifluoro-1-methyl-1-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, stirring at room temperature, chloroplatinic acid (H ₂ Pt
The reaction was initiated by adding 0.2 ml of a 0.2 molar solution of Cl ₆ ) in isopropyl alcohol. Then 10
After heating under reflux at 0 ° C. for 48 hours, the temperature was returned to room temperature, diluted with n-hexane, the reaction solution was subjected to suction filtration on Celite, and the solvent was distilled off under reduced pressure to obtain a crude product. Thereafter, the crude product was purified by distillation under reduced pressure at 3 mmHg and 98 ° C. to obtain 41 g of a compound. For this compound, ¹
When the H-NMR spectrum (chemical shift “σH”) and infrared absorption spectrum (IR) were measured, the measured values were as follows, and the above formula (I-1-5) (where Rf was trifluoromethyl The compound (I) is represented by the following formula: σH: 3.8 ppm (ethoxy group), 1.2 ppm
(Ethoxy group), 0.2 ppm (SiCH ₃ group). IR: 3400 cm ^-1 (hydroxyl group), 1218 cm
^-1 (CF bond), 1098 cm ^-1 (siloxane group).

Application Example 1 (Production of Polysiloxane Resin) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, the above-mentioned formula (I-1-6) (where Rf is a trifluoromethyl group) 2.5 g of 4-methyl-2-pentanone and 0.42 g of a 1.75% by weight aqueous oxalic acid solution were added, and the mixture was reacted at 80 ° C. for 6 hours with stirring. Thereafter, the reaction vessel was cooled with ice to stop the reaction, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and the water was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The layer was distilled off under reduced pressure to obtain a resin. This resin was measured for ¹ H-NMR spectrum (chemical shift “σH”), infrared absorption spectrum (IR), and weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) by gel permeation chromatography (GPC). As a result, it was as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups). IR: 3400 cm ^-1 (hydroxyl group), 1221 cm
^-1 (CF bond), 1130 cm ^-1 (siloxane group),
1080 cm ^-1 (siloxane group). Mw: 3,300.

Application Example 2 (Production of Polysiloxane Resin) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, the above-mentioned formula (I-1-6) (where Rf is a trifluoromethyl group) Wherein the hydrogen atom of the hydroxyl group in the compound represented by the formula (1) is substituted with a t-butoxycarbonyl group:
g, 1.5 g of 4-methyl-2-pentanone, 0.20 g of a 1.75% by weight aqueous solution of oxalic acid.
The reaction was performed at 5 ° C. for 5 hours. Thereafter, the reaction vessel was cooled with ice to stop the reaction, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and the water was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The layer was distilled off under reduced pressure to obtain a resin. About this resin, ¹ H-NMR spectrum (chemical shift “σH”), infrared absorption spectrum (IR)
The measured Mw and Mw were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups);
5 ppm (t-butoxycarbonyl group). IR: 1774 cm ^-1 (carbonate group), 1217
cm ^-1 (C-F bond), 1132cm ^-1 (siloxane group), 1082cm ^-1 (siloxane group). Mw: 7,500.

Application Example 3 (Production of Polysiloxane Resin) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, the above-mentioned formula (I-1-6) (where Rf is a trifluoromethyl group) 1.98 g of a compound represented by the formula: 2-t-
Butoxycarbonylethyltriethoxysilane 1.62
g, 2.41 g of methyltriethoxysilane, 6.0 g of 4-methyl-2-pentanone and 1.65 g of a 1.75% by weight aqueous oxalic acid solution were added, and the mixture was reacted at 80 ° C. for 6 hours with stirring. Thereafter, the reaction vessel was cooled with ice to stop the reaction, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and the water was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The layer was distilled off under reduced pressure to obtain a resin. The ¹ H-NMR spectrum (chemical shift “σH”), infrared absorption spectrum (IR) and Mw of this resin were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups);
5 ppm (t-butoxycarbonyl group), 0.2 ppm
(SiCH ₃ group). IR: 3400 cm ^-1 (hydroxyl group), 1703 cm
^-1 (carbonyl group), 1213 cm ^-1 (CF bond),
1130 cm ^-1 (siloxane group), 1080 cm ^-1 (siloxane group). Mw: 2,500.

Application Example 4 (Production of Polysiloxane Resin) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, the above-mentioned formula (I-2-6) (where Rf is a trifluoromethyl group) ), 4.0 g of 4-methyl-2-pentanone and 0.58 g of a 1.75% by weight aqueous oxalic acid solution were added, and the mixture was reacted at 80 ° C. for 6 hours with stirring. Thereafter, the reaction vessel was cooled with ice to stop the reaction, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and the water was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The layer was distilled off under reduced pressure to obtain a resin. The ¹ H-NMR spectrum (chemical shift “σH”), infrared absorption spectrum (IR) and Mw of this resin were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups). IR: 3400 cm ^-1 (hydroxyl group), 1220 cm
^-1 (CF bond), 1130 cm ^-1 (siloxane group),
1080 cm ^-1 (siloxane group). Mw: 2,200.

Application Example 5 (Production of Polysiloxane Resin) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, the above-mentioned formula (I-2-6) (where Rf is a trifluoromethyl group) Wherein the hydrogen atom of the hydroxyl group in the compound represented by the formula (1) is substituted with a t-butoxycarbonyl group.
g, 4-methyl-2-pentanone 5.0 g and 1.7
0.61 g of a 5% by weight aqueous oxalic acid solution was added, and while stirring,
The reaction was performed at 80 ° C. for 6 hours. Thereafter, the reaction vessel was cooled with ice to stop the reaction, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and the water was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The layers are distilled off under reduced pressure,
A resin was obtained. About this resin, ¹ H-NMR spectrum (chemical shift “σH”), infrared absorption spectrum (I
R) and Mw were measured and were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups);
5 ppm (t-butoxycarbonyl group). IR: 1775 cm ^-1 (carbonate group), 1220
cm ^-1 (C-F bond), 1130 cm ^-1 (siloxane group), 1080 cm ^-1 (siloxane group). Mw: 2,400.

Application Example 6 (Production of Polysiloxane Resin) A three-necked flask equipped with a stirrer, a reflux condenser and a thermometer was charged with the above formula (III-1-3) (provided that -Si (CH ₃ ) O -The number of units is 4.) 2.22 g of a compound represented by the following formula: 2.78 g of methyltriethoxysilane, 5.0 g of 4-methyl-2-pentanone and 1.4 g of a 1.75% by weight aqueous oxalic acid solution.
1 g was added, and the mixture was reacted at 80 ° C. for 6 hours with stirring. Thereafter, the reaction vessel was cooled with ice to stop the reaction, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and the water was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The layer was distilled off under reduced pressure to obtain a resin. For this resin, the ¹ H-NMR spectrum (chemical shift “σ
H "), infrared absorption spectrum (IR) and Mw were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups);
2 ppm (SiCH ₃ groups). IR: 3400 cm ^-1 (hydroxyl group), 1221 cm
^-1 (CF bond), 1311 cm ^-1 (siloxane group),
1078 cm ^-1 (siloxane group). Mw: 3,300.

Application Example 7 (Production of Polysiloxane Resin) A three-necked flask equipped with a stirrer, a reflux condenser and a thermometer was charged with the above formula (III-1-3) (provided that -Si (CH ₃ ) O -The number of units is 4.) A compound in which a hydrogen atom of a hydroxyl group in the compound represented by the formula (1) is substituted with a t-butoxycarbonyl group.
48 g, 2.52 g of methyltriethoxysilane, 5.0 g of 4-methyl-2-pentanone and 1.28 g of a 1.75% by weight aqueous oxalic acid solution were added thereto.
Allowed to react for hours. Thereafter, the reaction vessel was cooled with ice to stop the reaction, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and the water was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The layer was distilled off under reduced pressure to obtain a resin. The ¹ H-NMR spectrum (chemical shift “σH”), infrared absorption spectrum (IR) and Mw of this resin were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups);
5 ppm (t-butoxycarbonyl group), 0.2 ppm
(SiCH ₃ group). IR: 1775 cm ^-1 (carbonate group), 1221
cm ^-1 (C-F bond), 1131cm ^-1 (siloxane group), 1078cm ^-1 (siloxane group). Mw: 3,500.

Application Example 8 (Production of Polysiloxane Resin) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, the above-mentioned formula (I-1-5) (where Rf is a trifluoromethyl group) 4.0 g, 15 g of 4-methyl-2-pentanone and 0.72 g of a 1.75% by weight aqueous oxalic acid solution were added, and the mixture was reacted at 80 ° C. for 6 hours with stirring. Thereafter, the reaction vessel was cooled with ice to stop the reaction, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and the water was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The layer was distilled off under reduced pressure to obtain a resin. The ¹ H-NMR spectrum (chemical shift “σH”), infrared absorption spectrum (IR) and Mw of this resin were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups);
2 ppm (SiCH ₃ groups). IR: 3400 cm ^-1 (hydroxyl group), 1220 cm
^-1 (CF bond), 1130 cm ^-1 (siloxane group),
1080 cm ^-1 (siloxane group). Mw: 2,200.

Comparative Application Example 1 (Production of Polysiloxane Resin) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 20 g of 2-t-butoxycarbonylethyltriethoxysilane and 4-methyl-2- 60 g of pentanone and 4.09 g of a 1.75% by weight aqueous oxalic acid solution were added, and the mixture was reacted at 80 ° C. for 6 hours with stirring. Thereafter, the reaction vessel was cooled with ice to stop the reaction, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and the water was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The layer was distilled off under reduced pressure to obtain a resin. The ¹ H-NMR spectrum (chemical shift “σH”), infrared absorption spectrum (IR) and Mw of this resin were measured, and the results were as follows. σH: 1.5 ppm (t-butoxycarbonyl group). IR: 3400 cm ^-1 (hydroxyl group), 1703 cm
^-1 (carbonyl group), 1130 cm ^-1 (siloxane group), 1080 cm ^-1 (siloxane group). Mw: 2,700.

Evaluation Example 1 (Evaluation of Radiation Transmittance) Thickness of 1,000 形成 formed from each resin manufactured in Application Example 1, Application Example 2, Application Example 3, Application Example 4, Application Example 8, and Comparative Application Example 1. With respect to the film of No. 1, the radiation transmittance at wavelengths of 157 nm and 193 nm was measured. Table 1 shows the measurement results.

[0147]

[Table 1]

As is clear from Table 1, the polysiloxane resin obtained from the silicon-containing alicyclic compound of the present invention is:
Since the basic skeleton is a polysiloxane structure, the wavelength is 193.
Each of the radiation transmittances at nm shows a high value equal to or higher than that of the resin of Comparative Application Example 1. On the other hand, at a wavelength of 157 nm, the resin of Comparative Application Example 1 had a radiation transmittance of 30%, whereas the resins of Application Example 1, Application Example 2, Application Example 3, Application Example 4, and Application Example 8 had a radiation transmittance of 30%. All have a higher radiation transmittance than the resin of Comparative Application Example 1. The radiation transmittance at a wavelength of 157 nm is generally considered to be reduced by a relative increase in the proportion of the hydrocarbon structure in the polysiloxane resin, but the polysiloxane resin obtained from the silicon-containing alicyclic compound of the present invention is Although the ratio of the hydrocarbon structure is relatively large and the partial structure in the resin changes, the wavelength of 157 n
The radiation transmittance at m is at a high level.

Evaluation Example 2 (Evaluation of Resist Performance) Each of the resins obtained in Application Examples 1, 4 and 8 was evaluated as follows.
The heptanone solution was applied on a silicon wafer by a spin coater, and heated on a hot plate maintained at 130 ° C. for 90 seconds to form a 1,000-μm-thick film. Thereafter, when each coating was immersed in ion-exchanged water for 60 seconds, the thickness of the coating hardly changed. On the other hand, when each coating was immersed in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 60 seconds, the coating was completely dissolved and removed from the wafer. From these results, each resin obtained from the compound (I) and the compound (III) having a free hydroxyl group of the present invention shows the property of being insoluble or hardly soluble in ion-exchanged water, while the ordinary alkali developing It has high solubility in liquids and has sufficient utility as a resin component in a chemically amplified resist.

Further, 100 parts by weight of each resin obtained in Application Examples 2 and 3, 1 part by weight of triphenylsulfonium trifluoromethanesulfonate (radiation-sensitive acid generator), and tri-n-octylamine (acid diffusion control) Agent) 0.
02 parts by weight and 900 parts by weight of 2-heptanone (solvent) were uniformly mixed to prepare a composition solution. Next, each composition solution was applied on a silicon wafer by spin coating, and was applied to a hot plate maintained at 130 ° C. for 9 hours.
A heat treatment was performed for 0 second to form a resist film having a thickness of 100 nm. Then, for each resist film, Ar
Exposure was performed by changing the exposure amount using an F excimer laser (wavelength: 193 nm), and heat treatment was performed for 90 seconds on a hot plate maintained at 110 ° C., followed by development with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide. Then, a resist pattern was formed. As a result of observing each of the obtained resist patterns with a scanning electron microscope, the resin of Application Example 2 was resolved to 0.30 μm, and the resin of Application Example 3 was resolved to 0.15 μm. Was.

[0151]

The compound (I) of the present invention is extremely useful as a raw material for synthesizing the compound (II) of the present invention. Further, the compound (I) in which the total number of the halogen atom bonded to the silicon atom and the group OR ² is 2 or 3 is extremely useful as a raw material for producing an alkali-soluble polysiloxane resin. This alkali-soluble polysiloxane resin can be used very suitably for a positive or negative type chemically amplified resist, and these chemically amplified resists have dry etching resistance, transparency to radiation, resolution and development. It has excellent properties. The compound (II) of the present invention in which the total number of the halogen atom bonded to the silicon atom and the group OR ² is 2 or 3,
It is extremely useful as a raw material for producing a polysiloxane resin having an acid dissociable organic group. The polysiloxane resin having an acid-dissociable organic group can be used very suitably as a chemically amplified resist excellent in dry etching resistance, transparency to radiation, resolution, developability, and the like. The compound (III) of the present invention is particularly useful as a raw material for synthesizing the compound (IV) of the present invention. Compound (III) is also extremely useful as a raw material for producing an alkali-soluble polysiloxane resin. This alkali-soluble polysiloxane-based resin can be used very suitably for a positive or negative type chemically amplified resist.
It has excellent properties such as dry etching resistance, transparency to radiation, resolution, and developability. The compound (IV) of the present invention is extremely useful as a raw material for producing a polysiloxane resin having an acid-dissociable organic group. The polysiloxane-based resin having an acid-dissociable organic group can be extremely suitably used as a positive chemically amplified resist excellent in dry etching resistance, transparency to radiation, resolution, developability, and the like. Further, compound (I), compound (II), compound (III) and compound (I
V) is also useful as a raw material for polysiloxane-based resins in other technical fields and as a raw material for other silicon-containing alicyclic compounds having the same norbornane-based ring structure.

Continued on the front page F-term (reference) 4H049 VN01 VP01 VP03 VP04 VP05 VQ16 VQ21 VQ78 VR21 VR22 VR42 VR43 VU20 VU36 VW02 4J035 BA04 CA062 CA08M CA081 CA15M CA152 CA16M CA161 CA17M CA172 CA192 FB16 FB10 LB10 LB10 LB10

Claims (4)

[Claims] 1. A silicon-containing alicyclic compound represented by the following general formula (I). Embedded image [In the general formula (I), each R independently represents a hydrogen atom or a methyl group, and each R ¹ independently represents
A hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; a halogen atom; or a primary, secondary or tertiary amino group;
Each R ² is independently of each other a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or the following formula (i): (Wherein each X is independently a hydrogen atom;
20 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms.
It is an integer of 0. And m is 0 or 1, two R ² may be mutually bonded to form a ring together with two oxygen atoms and a silicon atom,
Represents a hydrogen atom, a methyl group or a trifluoromethyl group, m is an integer of 0 to 3, n is an integer of 0 to 3, and the silicon atom shown in the general formula (I) is at the top Bicyclo [2.2.1] 2-position or 3 of heptane ring
Attached to the − position. ] 2. A silicon-containing alicyclic compound having an acid dissociable organic group represented by the following general formula (II). Embedded image [In the general formula (II), each R independently represents a hydrogen atom or a methyl group, and each R ¹ independently represents
A hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; a halogen atom; or a primary, secondary or tertiary amino group;
Each R ² is independently of each other a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or a compound represented by the following formula (i): (Wherein each X is independently a hydrogen atom;
20 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms.
It is an integer of 0. And m is 0 or 1, two R ² may be mutually bonded to form a ring together with two oxygen atoms and a silicon atom,
Represents a hydrogen atom, a methyl group or a trifluoromethyl group; Z represents a monovalent acid-dissociable organic group; m is an integer of 0 to 3; n is an integer of 0 to 3; The silicon atom shown in II) is the bicyclo [2.2.
1] attached to the 2- or 3-position of the heptane ring. ] 3. A silicon-containing alicyclic compound represented by the following general formula (III). Embedded image [In the general formula (III), each R independently represents a hydrogen atom or a methyl group; each Y independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms; Carbon number 1
To 20 monovalent halogenated hydrocarbon groups; halogen atoms;
A primary, secondary or tertiary amino group; or -OR
^{2 wherein} R ² is a monovalent hydrocarbon group having 1 to 20 carbon atoms;
A monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or the following formula (i): (Wherein each X is independently a hydrogen atom;
20 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms.
It is an integer of 0. ). ｝ And R
f represents a hydrogen atom, a methyl group or a trifluoromethyl group, p is an integer of 3 to 10, n is an integer of 0 to 3, and each silicon atom represented by the general formula (III) is At the 2- or 3-position of the bicyclo [2.2.1] heptane ring. ] 4. A silicon-containing alicyclic compound having an acid dissociable organic group represented by the following general formula (IV). Embedded image [In the general formula (IV), each R independently represents a hydrogen atom or a methyl group, and each Y independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms; Carbon number 1
To 20 monovalent halogenated hydrocarbon groups; halogen atoms;
A primary, secondary or tertiary amino group; or -OR
^{2 wherein} R ² is a monovalent hydrocarbon group having 1 to 20 carbon atoms;
A monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or the following formula (i): (Wherein each X is independently a hydrogen atom;
20 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms.
It is an integer of 0. ). ｝ And R
f represents a hydrogen atom, a methyl group or a trifluoromethyl group; Z represents a monovalent acid-dissociable organic group;
And n is an integer of 0 to 3, and represented by the general formula (IV)
Are represented by the bicyclo [
2.2.1] attached to the 2- or 3-position of the heptane ring. ]